U.S. patent number 9,644,165 [Application Number 14/419,688] was granted by the patent office on 2017-05-09 for lubricating resin composition.
This patent grant is currently assigned to SUMITOMO SEIKA CHEMICALS CO., LTD.. The grantee listed for this patent is Sumitomo Seika Chemicals Co., Ltd.. Invention is credited to Tsuyoshi Masuda, Hitoshi Ozawa, Shinichi Takemori.
United States Patent |
9,644,165 |
Ozawa , et al. |
May 9, 2017 |
Lubricating resin composition
Abstract
The present invention provides a lubricating resin composition
for personal care, wherein the composition not only maintains its
excellent lubricity and roughness-resistant property under a wet
condition even during repeated use thereof, but also represents a
low swelling ratio and no slimy feeling under a wet condition. The
lubricating resin composition for personal care Of the present
invention comprises 100 parts by mass of a water-absorbent modified
polyalkylene oxide and 25 to 500 parts by mass of a low-melting
point polyamide resin.
Inventors: |
Ozawa; Hitoshi (Osaka,
JP), Takemori; Shinichi (Himeji, JP),
Masuda; Tsuyoshi (Himeji, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Sumitomo Seika Chemicals Co., Ltd. |
Kako-gun, Hyogo |
N/A |
JP |
|
|
Assignee: |
SUMITOMO SEIKA CHEMICALS CO.,
LTD. (Hyogo, JP)
|
Family
ID: |
50067939 |
Appl.
No.: |
14/419,688 |
Filed: |
July 26, 2013 |
PCT
Filed: |
July 26, 2013 |
PCT No.: |
PCT/JP2013/070363 |
371(c)(1),(2),(4) Date: |
February 05, 2015 |
PCT
Pub. No.: |
WO2014/024706 |
PCT
Pub. Date: |
February 13, 2014 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20150184106 A1 |
Jul 2, 2015 |
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Foreign Application Priority Data
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|
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Aug 10, 2012 [JP] |
|
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2012-178432 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61L
29/14 (20130101); C10M 107/44 (20130101); C08L
77/02 (20130101); A61L 29/049 (20130101); C08G
18/4833 (20130101); C08G 18/485 (20130101); C08L
77/06 (20130101); C08G 18/6674 (20130101); C08L
77/06 (20130101); C08L 75/08 (20130101); C08L
77/02 (20130101); C08L 75/08 (20130101); A61L
29/049 (20130101); C08L 71/02 (20130101); A61L
29/049 (20130101); C08L 77/02 (20130101); A61L
29/049 (20130101); C08L 77/06 (20130101); A61L
2400/10 (20130101); C10M 2209/04 (20130101) |
Current International
Class: |
C10M
107/44 (20060101); C08G 18/66 (20060101); C08G
18/48 (20060101); A61L 29/04 (20060101); A61L
29/14 (20060101); C08L 77/02 (20060101); C08L
77/06 (20060101); C10M 107/24 (20060101) |
Field of
Search: |
;508/386 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2447325 |
|
May 2012 |
|
EP |
|
54-094961 |
|
Jul 1979 |
|
JP |
|
04-507054 |
|
Dec 1992 |
|
JP |
|
07-024156 |
|
Jan 1995 |
|
JP |
|
09-502632 |
|
Mar 1997 |
|
JP |
|
10-248919 |
|
Sep 1998 |
|
JP |
|
10-248921 |
|
Sep 1998 |
|
JP |
|
2001-527027 |
|
Dec 2001 |
|
JP |
|
2004-509207 |
|
Mar 2004 |
|
JP |
|
2008-540647 |
|
Nov 2008 |
|
JP |
|
WO 2010150875 |
|
Dec 2010 |
|
JP |
|
02/30365 |
|
Apr 2002 |
|
WO |
|
Other References
Notification of Transmittal of Translation of The International
Preliminary Report on Patentability (Form PCT/IB/338) of
International Application No. PCT/JP2013/070363 mailed Feb. 19,
2015 with Forms PCT/IB/373 and PCT/ISA/237 (9 pages). cited by
applicant .
Notification Concerning Transmittal of International Preliminary
Report on Patentability (Form PCT/IB/326) of International
Application No. PCT/JP2013/070363 mailed Feb. 19, 2015 with Forms
PCT/IB/373 and PCT/ISA/237 (in Japanese) (7 pages). cited by
applicant .
Extended European Search Report dated Feb. 16, 2016, issued in
counterpart European Application No. 13827485.7 (8 pages). cited by
applicant .
International Search Report dated Oct. 1, 2013, issued in
corresponding application No. PCT/JP2013/070363. cited by
applicant.
|
Primary Examiner: Goloboy; James
Attorney, Agent or Firm: Westerman, Hattori, Daniels &
Adrian, LLP
Claims
The invention claimed is:
1. A lubricating resin composition for personal care, wherein the
composition comprises 100 parts by mass of a water-absorbent
modified polyalkylene oxide and 50 to 400 parts by mass of a
low-melting point polyamide resin, wherein the low-melting point
polyamide resin is a polyamide resin having a melting point of
160.degree. C. or lower, wherein a water absorption ability of the
water-absorbent modified polyalkylene oxide is 10 to 40 [g/g].
2. The lubricating resin composition for personal care according to
claim 1, wherein the water-absorbent modified polyalkylene oxide is
a modified polyalkylene oxide obtained by reacting a polyalkylene
oxide compound, a diol compound and a diisocyanate compound with
each other.
3. The lubricating resin composition for personal care according to
claim 1, wherein a ratio of a water-soluble component of the
water-absorbent modified polyalkylene oxide is 5 to 30% by
mass.
4. The lubricating resin composition for personal care according to
claim 1, wherein the low-melting point polyamide resin is polyamide
obtained by polymerizing raw materials comprising at least one type
of raw material for polyamide selected from the group consisting of
nylon 6, nylon 66, nylon 610, nylon 11, and nylon 12, or a
combination of two or more types of the polyamide.
Description
TECHNICAL FIELD
The present invention relates to a lubricating resin composition
whose lubricity is achieved under a wet condition, especially, a
lubricating resin composition for use in personal care items to be
used in contact with a skin. The present invention more
particularly relates to a lubricating resin composition for
personal care obtained by mixing a water-absorbent modified
polyalkylene oxide with a low-melting point polyamide resin.
BACKGROUND ART
For a personal care item such as a razor, a razor blade cartridge
has conventionally been proposed, which comprises a shaving aid
containing a water-soluble resin such as a polyalkylene oxide
attached to a portion of the razor blade cartridge made of plastic,
in order to reduce the resistive force between a portion of a razor
and the facial surface, etc., (for example, Patent Document 1).
It is known that a high-molecular weight compound (water-soluble
resin) obtained by reacting a polyalkylene oxide compound and a
diisocyanate with each other and having a weight-average molecular
weight of 10000 or higher is used as a water-soluble solidified
shaving aid (Patent Document 2).
A composite may be used as a smoother (lubricating agent) for wet
shaving, wherein the composite comprises a water-swellable polymer
swelling and releasing various aids upon immersion of the composite
in water due to mixing of a water-soluble polymer (water-soluble
resin) and the water-swellable polymer (Patent Document 3).
A polymer composite is disclosed as a polymer composite used in wet
shaving instruments, medical instruments, etc., wherein the polymer
composite comprises a water-insoluble polymer, and a
water-sensitive copolymer (water-soluble resin) obtained by
polymerizing an alkylene oxide monomer and an epoxy-functional
monomer (Patent Document 4).
PRIOR ART DOCUMENT
Patent Documents
Patent Document 1: JP 54-94961 A
Patent Document 2: JP 07-24156 A
Patent Document 3: JP 09-502632 A
Patent Document 4: JP 2004-509207 A
SUMMARY OF THE INVENTION
Problem to be Solved
The razor blade cartridge described in Patent Document 1, the
composite described in Patent Document 3, and the polymer composite
described in Patent Document 4 each utilize elution of the
water-soluble resin under a wet condition to give lubricity to the
surfaces of the cartridge.
However, when a desired member is formed by melt-mixing the
water-soluble resin and a thermoplastic resin, the water-soluble
resin is scattered in blocks in the surface of the member since the
compatibility between the water-soluble resin and the thermoplastic
resin is low. For this reason, lubricity at the initial stage of
use is excellent while the scattered water-soluble resin is dropped
in blocks by repeated use, and the lubricity is lost in a short
time.
The shaving aid described in Patent Document 2 and comprising the
high-molecular weight compound is excellent in water-solubility,
and the water-soluble component thereof therefore flows out at one
time by an amount equal to or more than a necessary amount. Thus,
the following problems arise: that the skin becomes slimy; that the
water-soluble component of the compact drops off to cause
contraction and hardening during repeated use thereof resulting in
degradation of the durability thereof; and the like. Although
mixing with another resin is also examined in order to improve
durability, another problem arises that the compatibility
therebetween is low.
A water-soluble resin such as a polyalkylene oxide generally has
more excellent lubricity as the molecular weight thereof increases,
while cobwebbing thereof under a wet condition becomes more
remarkable and the melt viscosity thereof becomes higher. Thus, it
is necessary to raise the temperature for the processing. For this
reason, the high-molecular weight water-soluble resin is often
mixed with a polymer having a low hydrophilic property and low
flexibility such as high impact polystyrene or polystyrene each
having a high processing temperature. The mixture thus obtained is
excellent in lubricity under a wet condition, while high impact
polystyrene or polystyrene themselves do not adapt to water and
have low flexibility, causing therefore problems to arise that the
composition has low adhesiveness to the skin and that a roughness
resistant property thereof is degraded because feeling of roughness
is generated on the surface thereof due to the dropping off of the
water-soluble resin component during repeated use. When the
water-soluble resin is increased in order to maintain the good
lubricity, the swelling ratio under a wet condition is increased,
and thus, when the composition is then dried in the repeated use,
another problem arises that the surface of the composition is
deformed to have recesses and protrusions.
On the other hand, a resin which is familiar with water and
represents a good touch can be highly hydrophilic nylon, but the
processing temperature of general nylons are high compared with
those of high impact polystyrene and polystyrene. Thus, when nylon
and a polyalkylene oxide are simultaneously used, the polyalkylene
oxide is decomposed during the processing and becomes colored, and
the molecular weight thereof is reduced. A problem therefore arises
that the lubricity thereof is degraded, and the like. In order to
solve this problem, it is also examined to mix low-melting point
nylon with a high-molecular weight polyalkylene oxide. However, the
high-molecular weight polyalkylene oxide has high melt viscosity,
and a problem arises in their compatibility that the high-molecular
weight polyalkylene oxide does not sufficiently dissolve at the
mixing temperature in its mixing with low-melting point nylon, and
only disperses in the form of dispersed powders in low-melting
point nylon, resulting in difficulty for the effect (lubricity) to
be achieved, etc.
An object of the present invention is to provide a lubricating
resin composition for personal care, wherein the composition not
only maintains its excellent lubricity and roughness resistant
property under a wet condition even during repeated use thereof,
but also has a low swelling ratio and represents no slimy feeling
under a wet condition.
Means to Solve the Problems
The inventors has actively studied to solve the above problems, and
as a result, found that a lubricating resin composition comprising
a water-absorbent modified polyalkylene oxide and a specific
polyamide resin mixed therein was excellent in lubricity and
roughness resistant property and represented good deformation
resistance under a dry condition, and the inventors has achieved
the present invention.
The present invention relates to a lubricating resin composition
for personal care, wherein the composition comprises 100 parts by
mass of a water-absorbent modified polyalkylene oxide and 25 to 500
parts by mass of a low-melting point polyamide resin.
Effect of the Invention
The lubricating resin composition of the present invention can
maintain its excellent lubricity and roughness resistant property
under a wet condition even during repeated use thereof. In
addition, the lubricating resin composition of the present
invention represents a good deformation resistance under a dry
condition due to its relatively low swelling ratio under a wet
condition. Furthermore, the lubricating resin composition of the
present invention represents no slimy feeling under a wet
condition. The lubricating resin composition of the present
invention comprises the low-melting point polyamide, and therefore
represents a good touch having a moist feeling even under a dry
condition. As a result, the lubricating resin composition of the
present invention is widely usable for personal care items such as
wet shaving instruments typified by a razor, and medical
instruments such as a catheter.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic diagram of a method of determining a mean
coefficient of friction (MIU).
FIG. 2 is a schematic diagram of a method of determining a
deviation in the mean coefficient of friction (MMD).
MODES FOR CARRYING OUT THE INVENTION
The lubricating resin composition of the present invention
comprises a water-absorbent modified polyalkylene oxide and a
low-melting point polyamide resin.
The water-absorbent modified polyalkylene oxide used in the
lubricating resin composition of the present invention is, for
example, a modified polyalkylene oxide obtained by reacting a
polyalkylene oxide compound, a diol compound and a diisocyanate
compound with each other. The water-absorbent modified polyalkylene
oxide has low melt viscosity and is thermoplastic. The
water-absorbent modified polyalkylene oxide thus has good
compatibility with a polyamide resin, compared with water-soluble
resins such as a polyalkylene oxide.
The polyalkylene oxide compound for producing the water-absorbent
modified polyalkylene oxide is a homopolymer or a copolymer
comprising one, or two or more type (s) of alkylene oxide group
selected from the group consisting of preferably alkylene oxide
groups having 2 to 9 carbon atoms and more preferably alkylene
oxide groups having 2 to 4 carbon atoms. Preferable specific
examples of the alkylene oxide group include ethylene oxide,
1,2-propylene oxide, 1,3-propylene oxide, isobutylene oxide,
1,2-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide,
trimethylethylene oxide, tetramethylethylene oxide, cyclohexene
oxide, oxetane, tetrahydrofuran, tetrahydropyran, 1,2-pentene oxide
and 1,2-hexene exide. The polyalkylene oxide compound may be used
alone, and two or more types thereof may also be used in
combination.
The polyalkylene oxide compound is preferably a polyalkylene oxide
compound comprising 90% by mass or more of ethylene oxide groups
and more preferably a polyalkylene oxide compound comprising 95% by
mass or more of ethylene oxide groups, from the viewpoint of
further improvement in lubricity of the lubricating resin
composition in the initial state. Each of these ratios is a value
relative to the overall weight of the polyalkylene oxide
compound.
The polyalkylene oxide compound is preferably a polyalkylene oxide
compound having a number average molecular weight of 5000 to 50000,
and more preferably a polyalkylene oxide compound having a number
average molecular weight of 10000 to 30000, from the viewpoint of
further improvement in lubricity of the lubricating resin
composition in the initial state and during its repeated use.
The dial compound for producing the water-absorbent modified
polyalkylene oxide is one, or two or more type(s) of diol selected
from the group consisting of preferably dials having 2 to 9 carbon
atoms and more preferably dials having 2 to 5 carbon atoms.
Specific examples of the dial compound include aliphatic diol
compounds such as ethylene glycol, diethylene glycol, triethylene
glycol, tetraethylene glycol, propylene glycol, dipropylene glycol,
trimethylene glycol, 1,3-butanediol, 2,3-butanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,9-nonanediol.
Among these diol compounds, ethylene glycol and 1,4-butanediol are
suitably used from the viewpoints that the obtained water-absorbent
modified polyalkylene oxide is excellent in water absorption
ability, that elution of a water-soluble component therefrom is
suppressed, and that stability thereof is excellent. The dial
compound may be used alone, and two or more types thereof may also
be used in combination.
The used amount of the diol compound preferably is from 0.8 to 2.5
mol and more preferably from 1.0 to 2.0 mol, relative to 1 mol of
the polyalkylene oxide compound, from the viewpoint of water
absorption ability of the water-absorbent modified polyalkylene
oxide. The molar number of the polyalkylene oxide compound can be
determined by dividing the mass thereof by the number average
molecular weight thereof.
The diisocyanate compound is not particularly limited only when the
diisocyanate compound is a compound having two isocyanate groups
(--NCO) in one same molecule. Examples thereof include aromatic
diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI),
1,8-dimethylbenzol-2,4-diisocyanate and 2,4-tolylene diisocyanate
(TDI); aliphatic diisocyanates such as 1,6-hexamethylene
diisocyanate (HDI); and alicyclic diisocyanate such as
dicyclohexylmethane-4,4'-diisocyanate (HMDI) and
3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI).
Among these diisocyanate compounds, aliphatic diisocyanates and
alicyclic diisocyanates are suitably used from the viewpoints of
the compatibility with polyamide resins, suppression of elution of
a water-soluble compound, and excellent stability, and
dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene
diisocyanate (HDI) are more suitably used. The diisocyanate
compound may be used alone, and two or more types thereof may also
be used in combination.
The ratio in use of each of the polyalkylene oxide compound, the
diol compound, and the diisocyanate compound is determined such
that the ratio of the molar number of isocyanate groups of the
diisocyanate compound relative to the total molar number of
terminal hydroxyl groups of the polyalkylene oxide compound and
hydroxyl groups of the diol compound [R value=(--NCO group/--OH
group)] is preferably in a range of 0.7 to 1.2 and more preferably
in a range of 0.8 to 1.05, from the viewpoint of further
improvement in each of the lubricity during repeated use, and the
compatibility between the water-absorbent modified polyalkylene
oxide and the polyamide resin. The molar number of the isocyanate
groups of the diisocyanate compound can be determined by doubling
the value obtained by dividing the mass of the diisocyanate
compound by its number average molecular weight.
Examples of methods of reacting the polyalkylene oxide compound,
the dial compound and the diisocyanate compound with each other
include a method of dissolving or dispersing all the compounds in a
reaction solvent such as toluene, xylene or dimethylformamide to
cause the compounds to react; and a method of uniformly mixing all
the compounds in a powder state or a solid state, and then heating
the mixture to a predetermined temperature to cause the compounds
to react in a molten state. From the viewpoint of the industrial
implementation, preferable is a method of continuously supplying
the raw materials in the molten state, and mixing the raw materials
in a multi-screw extruder to cause the raw materials to react. The
temperature of the reaction is preferably from 70 to 210.degree.
C.
When the water-absorbent modified polyalkylene oxide is produced,
from the viewpoint of promoting the reaction, a small amount of
triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin
dilaurate, tin 2-ethylhexanoate, triethylenediamine or the like may
also be added to the reaction system.
Thus, the water-absorbent modified polyalkylene oxide can be
obtained by reacting the polyalkylene oxide compound, the diol
compound and the diisocyanate compound. A urethane group is formed
in the water-absorbent modified polyalkylene oxide from the
reaction between an isocyanate group and a hydroxyl group, and an
interaction acts between the urethane group and an amide group of
the low-melting point polyamide resin described later. Thereby, the
compatibility is improved between the water-absorbent modified
polyalkylene oxide and the low-melting point polyamide resin. It
can be considered that excellent lubricity and roughness resistant
property during the repeated use, the relatively low swelling ratio
under a wet condition, and the good deformation resistance under a
dry condition are achieved due to this improvement of the
compatibility.
The water absorption ability of the water-absorbent modified
polyalkylene oxide used in the lubricating resin composition of the
present invention is preferably from 10 to 40 [g/g], and more
preferably from 15 to 35 [g/g]. If the water absorption ability of
the water-absorbent modified polyalkylene oxide is lower than 10
[g/g], the lubricity and the roughness resistant property in the
initial stage of use of and during repeated use of the obtained
lubricating resin composition may be degraded. If the water
absorption ability of the water-absorbent modified polyalkylene
oxide is higher than 40 [g/g], the degree of maintenance of the
lubricity may be lowered during repeated use of the obtained
lubricating resin composition. The "water absorption ability" in
the present invention is a value measured using a method described
later.
The ratio of the water-soluble component of the water-absorbent
modified polyalkylene oxide used in the present invention is
preferably from 5 to 30% by mass and more preferably from 10 to 20%
by mass, relative to the mass of the water-absorbent modified
polyalkylene oxide, from the viewpoint of improving lubricity of
the obtained lubricating resin composition. The "ratio of the
water-soluble component" in the present invention is a value
measured by a method described later.
From the viewpoint of further improvement of each of the initial
lubricity and the compatibility with the polyamide resin, the melt
viscosity of the water-absorbent modified polyalkylene oxide used
in the lubricating resin composition of the present invention is
preferably from 100 to 800 [Pas] and more preferably from 100 to
400 [Pas] when the melt viscosity is measured by means of a flow
tester (constant test force extrusion type capillary rheometer)
(conditions: 170.degree. C., 5.0 MPa, a die having a diameter of 1
mm.times.a length of 1 mm is used). In this case, the melt
viscosity ratio with the melt viscosity of the low-melting point
polyamide resin (under the same conditions) (the low-melting point
polyamide resin/the water-absorbent modified polyalkylene oxide) is
preferably from 0.1 to 0.8, and more preferably from 0.2 to
0.6.
The low-melting point polyamide resin used in the lubricating resin
composition of the present invention is preferably a polyamide
resin having a melting point of 160.degree. C. or lower. If a
polyamide resin having a melting point higher than 160.degree. C.
(nylon) is used, the water-absorbent modified polyalkylene oxide
tends to be modified during the mixing, and the lubricating resin
composition may be obtained which does not have good lubricity from
the initial stage. More preferably, the melting point thereof is
from 80 to 150.degree. C.
Preferably, the low-melting point polyamide resin having a melting
point of 160.degree. C. or lower is a polyamide obtained by
polymerizing at least one type of raw material for a polyamide
selected from the group consisting of nylon 6 (polycaprolactam),
nylon 66 (polyhexamethyleneadipamide), nylon 610
(polyhexamethylenesebacamide), nylon 11 (polyundecaneamide), and
nylon 12 (polylauryllactam). More preferably, a polyamide is used
which is obtained by copolymerizing at least two types of the above
raw materials for polyamide, and example of the copolymerized
polyamide include binary copolymers such as nylon 6/nylon 12 ("/"
indicates that the material is a copolymer) and nylon 610/nylon 12,
ternary copolymers such as nylon 6/nylon 66/nylon 12, nylon 6/nylon
610/nylon 12 and nylon 66/nylon 610/nylon 12, and a multicomponent
copolymer such as nylon 6/nylon 66/nylon 610/nylon 12. The
low-melting point polyamide resin may be a polyamide obtained by
copolymerizing the above raw material for polyamide and a raw
material including a raw material different from the above raw
materials for polyamide. The low-melting point polyamide resin may
be used alone, and two or more types thereof may also be used in
combination. The specific names of commercially available products
as the low-melting point polyamide resin can be "Amilan 842P-48",
"Amilan 842P-70" and "Amilan 842P-80" (manufactured by Toray
Industries, Inc.), and also "Griltex D1500A" and "Griltex D1666A"
(manufactured by EMS Japan, Ltd.). The "melting point" refers to a
melting peak temperature (.degree. C.) measured by means of a
differential scanning calorimeter (DSC) at a temperature increase
rate of 10.degree. C./min.
The melt viscosity of the low-melting point polyamide resin is
preferably from 60 to 300 [Pas] and more preferably 50 to 150
[Pas], the melt viscosity being measured by means of a flow tester
(constant test force extrusion type capillary rheometer)
(conditions: 170.degree. C., 5.0 MPa, a die having a diameter of 1
mm.times.a length of 1 mm is used).
The melt flow rate (MFR) of the low-melting point polyamide resin
(conditions: 160.degree. C., 21.18 N) is preferably from 10 to 120
[g/min] and more preferably from 15 to 100 [g/min].
The ratio of the used low-melting point polyamide resin is 25 parts
by mass or higher and preferably 50 parts by mass or higher,
relative to 100 parts by mass of the water-absorbent modified
polyalkylene oxide. The ratio of the used low-melting point
polyamide resin is 500 parts by mass or lower, and preferably 400
parts by mass or lower, relative to 100 parts by mass of the
water-absorbent modified polyalkylene oxide. For example, the ratio
of the used low-melting point polyamide resin is from 25 to 500
parts by mass and preferably from 50 to 400 parts by mass, relative
to 100 parts by mass of the water-absorbent modified polyalkylene
oxide.
In the case where the ratio of the used low-melting point polyamide
resin is less than 25 parts by mass, if the obtained lubricating
resin composite is brought into contact with water, the swelling
ratio for water is high and the dimensions are significantly varied
by the swelling. Thereafter, when the lubricating resin composition
is dried during the repeated use, the surface of the composition is
deformed to have protrusions and recesses. In the case where that
the ratio of the used low-melting point polyamide resin exceeds 500
parts by mass, lubricity of the obtained lubricating resin
composition is degraded in the initial stage.
In addition to the low-melting point polyamide resin, other
polymers having good compatibility with the water-absorbent
modified polyalkylene oxide may be also used, such as an
ethylene/vinyl acetate copolymer, an ethylene/acrylic acid
copolymer and an ethylene/ethyl acrylate copolymer. Simultaneous
use of these copolymers improves flexibility of the obtained
lubricating resin composition. The ratio of the other polymer used
therein is 500 parts by mass or lower and preferably from 100 to
300 parts by mass, relative to 100 parts by mass of the
water-absorbent modified polyalkylene oxide.
Examples of a method of producing the lubricating resin composition
of the present invention include 1) a method wherein the
water-absorbent modified polyalkylene oxide, the low-melting point
polyamide resin and optionally the other polymer are used each by a
predetermined amount and mixed in advance by means of a mixing
machine such as a Henschel mixer or a blender and, then the mixture
is supplied to a kneader, a roll, an extruder or the like, and is
melt-mixed; 2) a method wherein the water-absorbent modified
polyalkylene oxide, the low-melting point polyamide resin and
optionally the other polymer are each supplied by a predetermined
amount to a kneader, a roll, an extruder or the like by means of a
metering feeder or the like, and are melt-mixed; and 3) a method
wherein the polyalkylene oxide compound, the diol compound and the
diisocyanate compound are caused to react with each other in the
low-melting point polyamide resin melted in advance.
A twin-screw extruder is suitably used as the machine for
performing the melt-mixing process, the melting process and/or the
reaction process, from the viewpoint of its excellent mixability
for the components.
After the melt-mixing process or the reaction process, the mixture
may be also molded into a desired shape such as a pellet, a sheet,
a bar or a fiber by executing injection molding or extrusion
molding. The lubricating resin composition of the present invention
may thus have the figure of a raw material such as a pellet or may
have the figure of a desired compact such as a sheet, a bar or a
fiber.
When the lubricating resin composition according to the present
invention is produced, a stabilizer may be also added from the
viewpoint of preventing resolution of each of the components and
the obtained lubricating resin composition; a UV absorber may be
also added from the viewpoint of improving the weather resistance
of the obtained lubricating resin composition; a pigment, a
coloring material or the like may be also added from the viewpoint
of coloring the obtained lubricating resin composition; and a soap
basis or the like may be also added from the viewpoint of imparting
foamability to the obtained lubricating resin composition.
In addition, water-soluble polyalkylene oxide may be also added
from the viewpoint of improving the adhesiveness to the skin.
Water-soluble polyalkylene oxide is excellent in the compatibility
with the water-absorbent modified polyalkylene oxide, and can
therefore be uniformly dispersed even at a processing temperature
of the low-melting point polyamide resin (low processing
temperature).
The lubricating resin composition of the present invention is
useful for applications in which achievement of lubricity under a
wet condition is necessary, and is useful for personal care
applications such as wet shaving instruments typified by a razor,
and medical instruments such as a catheter.
For example, when the lubricating resin composition of the present
invention is used in a wet shaving instrument (razor), the
lubricating resin composition constitutes a so-called shaving aid
unit which is arranged in substantially parallel to a razor blade
in a face for attaching the razor blade in the razor or its
cartridge (hereinafter, referred to as "razor or the like").
Thereby, the razor or the like comprising the lubricating resin
composition of the present invention can maintain its excellent
lubricity and roughness resistant property under a wet condition
even during its repeated use. The shaving aid unit in the razor or
the like has relatively low swelling ratio under a wet condition,
and thus represents a good deformation resistance under a dry
condition. The shaving aid unit represents no slimy feeling under a
wet condition. The shaving aid unit comprises the low-melting point
polyamide resin having high hydrophilicity, and thus represents
moist and good touch feeling, and good feeling to skin even under a
dry condition.
For example, when the lubricating resin composition of the present
invention is used in a catheter, the lubricating resin composition
is arranged on the surface of a stent or a guide wire used for a
resin in contact with a living tissue in the catheter. Thereby, the
catheter with the lubricating resin composition of the present
invention achieves the same effect as achieved when the lubricating
resin composition is used in the shaving aid unit of the razor or
the like.
EXAMPLES
The present invention will be described below in further detail by
Examples and Comparative Examples. However, the present invention
is not limited to these.
[Evaluation Methods]
Measurement and evaluation were executed according to the following
methods for the water absorption ability, the ratio of the
water-soluble component, and the melt viscosity of the
water-absorbent modified polyalkylene oxide described in each of
Production Examples, and the swelling ratio, the thickness
variation, the slimy feeling and the friction physical property of
the lubricating resin composition obtained in each of Examples and
Comparative Examples.
(1) Water Absorption Ability
The water absorption ability of the water-absorbent modified
polyalkylene oxide was measured using the following method.
About 1 [a] of the water-absorbent modified polyalkylene oxide (in
a pellet form) was weighed (A [g]), and then was immersed in 100
[mL] of ion exchange water measured in a 200-mL beaker under room
temperature (22.degree. C.) for 24 hours to gel. The gel was then
filtered using a 200-mesh wire gauze (pore size: 75 .mu.m) and the
mass thereof (B [g]) was measured. The water absorption ability was
calculated according to the following formula. Water absorption
ability [g/g]=B/A (2) Ratio of Water-Soluble Component
The gel obtained in the measurement of (1) Water Absorption Ability
was dried in a hot air dryer set at 105.degree. C. to a constant
weight (C [g]), and the ratio of the water-soluble component was
calculated according to the following formula. "A" is defined in
the same manner as "A" in the measurement of (1) Water Absorption
Ability. Ratio of water-soluble component [% by
mass]=(A-C)/A.times.100 (3) Melt Viscosity
The measurement was executed for 1.5 g of the water-absorbent
modified polyalkylene oxide or the like by means of a flow tester
(constant test force extrusion type capillary rheometer,
manufactured by Shimadzu Corporation, Model: CFT-500C) under the
following conditions.
Load: 5.0 MPa
Measurement Temperature: 170.degree. C.
Die Diameter: 1 mm
Die Length: 1 mm
(4) Swelling Ratio
The sheets of the lubricating resin composition obtained in
Examples and Comparative Examples were each cut into a sheet of 2
cm (W).times.5 cm (L) to be used as a measurement sample.
The mass (E [g]) of the measurement sample was measured, and the
sample was then immersed in 100 [mL] of ion exchange water measured
in a 200-mL beaker under room temperature (22.degree. C.) for 24
hours to swell. The measurement sample was then taken out, and the
water on the sample surface was wiped off with a paper towel to
measure the mass (F [g]) thereof. When the swelling ratio is lower
than 500%, it can be determined that the variation in dimensions
due to swelling is small. Swelling Ratio [%]=(F-E)/E.times.100 (5)
Thickness Variation
The thickness (D2) was measured for the sample whose swelling ratio
was measured, and was divided by the original thickness (D1) to
obtain the thickness variation. When the thickness variation is
equal to or smaller than four times, it can be determined that the
variation is small. Thickness Variation [times]=D2/D1
(6) Slimy Feeling
The sheets of the lubricating resin composition obtained in
Examples and Comparative Examples were each cut into a sheet of 2
cm (W).times.5 cm (L) to be used as a measurement sample.
Each of the measurement samples obtained in Examples or the like
was immersed in 100 mL of ion exchange water measured in a 200-mL
beaker for 1 minute, and the water on the sample surface was then
wiped off with a paper towel. The surface of the measurement sample
was rubbed with hand, and the evaluation was executed according to
the following evaluation criteria.
Evaluation Criteria
A: No slimy feeling was felt.
B: No cobwebbing occurred while slimy feeling was felt.
C: Slimy feeling was felt and cobwebbing occurred.
(7) Friction Physical Property
The sheets of the lubricating resin composition obtained in
Examples and Comparative Examples were each cut into a sheet of 2
cm (N).times.5 cm (L) to be used as a measurement sample.
0.2 mL of ion exchange water was added dropwise onto a coating
surface of each of the measurement samples, and the measurement
samples were left still for 30 seconds, 5 minutes, or 10 minutes
under the conditions of 25.degree. C. and 60% R.H. The friction
coefficient .mu. was then monitored by means of a friction tester
(manufactured by KATO TECH CO., LTD., Model: KES-SE) under the
following test conditions (first monitoring).
Sensor: silicone
Load: 50 [g]
Velocity: 10 [mm/sec]
(i) Mean Coefficient of Friction (MIU) (Lubricity)
The mean coefficient of friction has correlation with ease of
slipping and resistance against slipping felt in rubbing the
surface. The surface is more difficult to slip on as the value
become greater.
A schematic view is shown in FIG. 1 for obtaining a mean
coefficient of friction (MIU) from a result of the monitoring of
friction coefficient .mu..
As shown in FIG. 1, the surface of the measurement sample is
scanned for monitoring friction coefficient .mu. of the surface.
The friction coefficient .mu. is integrated for a width of 20 mm
for the monitoring (shaded area of FIG. 1). The mean coefficient of
friction (MIU) is obtained by dividing the integral value by the
width (20 mm) for the monitoring.
When the value of MIU is 0.10 or lower, the value is in such a
range that no problem arises in the practical use. When the value
is 0.02 or lower, its lubricity is good. When the value is 0.01 or
lower, its lubricity is best.
(ii) Deviation in Mean Coefficient of Friction (MMD) (Roughness
Resistant Property)
The deviation in the mean coefficient of friction has correlation
with smoothness and roughness felt in rubbing the surface. The
surface is rougher as this value becomes greater.
A schematic diagram is shown in FIG. 2 for determining the
deviation in the mean coefficient of friction (MMD) from results of
the monitoring of the friction coefficient.
As shown in FIG. 2, an absolute value of a difference between the
mean coefficient of friction (MIU) and the friction coefficient
.mu. is integrated for the width of 20 mm for monitoring (shaded
area of FIG. 2). The deviation in the mean coefficient of friction
(MMD) is obtained by dividing the integral value by the width for
the monitoring (20 mm).
When the value of MMD is from 0.001 to 0.015, the smoothness of the
surface is good.
When the value of MMD is 0.015 or lower, the value is in such a
range that no problem arises in the practical use. When the value
is 0.010 or lower, the smoothness of the surface is good. When the
value of MMD is 0.005 or lower, the smoothness of the surface is
best.
(iii) Repetition Test
After the first monitoring, the sheet was placed in an oven whose
temperature was set at 50.degree. C. for one hour to dry. Second
monitoring was then performed under the same conditions as
mentioned above. The monitoring was repeated up to a sixth time
with the same procedure, and the mean coefficient of friction and
its deviation were determined.
Production Example 1: Production of Water-Absorbent Modified
Polyalkylene Oxide
One hundred parts by mass of a fully dehydrated polyethylene oxide
having a number average molecular weight of 20,000, 0.90 parts by
mass of 1,4-butanediol and 0.1 part by mass of dioctyltin dilaurate
were put at these ratios into storage tank A equipped with a
stirrer and held at 80.degree. C., and were stirred in a nitrogen
gas atmosphere to obtain a uniform mixture. Separately,
dicycrohexylmethane-4,4'-diisocyanate was put into storage tank B
held at 30.degree. C., and was stored in a nitrogen gas
atmosphere.
The mixture in storage tank A was continuously supplied at a rate
of 500 [g/min], and dicyclohexylmetahane-4,4'-disisocyanate in
storage tank B was continuously supplied at a rate of 19.4 [g/min]
to a twin-screw extruder set at 110 to 140.degree. C. (R
value=1.00) by means of a metering pump, and these were mixed in
the extruder to perform a reaction. A strand was then discharged
through an exit of the extruder, and was pelletized (into blocks
each of 4.times.4.times.2.5 mm) by means of a pelletizer to obtain
a water-absorbent modified polyalkylene oxide.
The obtained water-absorbent modified polyalkylene oxide had a
water absorption ability of 25 [g/g], a ratio of the water-soluble
component of 15.5 [% by mass], and a melt viscosity of 320
[Pas]
Production Example 2: Production of Water-Absorbent Modified
Polyalkylene Oxide
An ethylene oxide/propylene oxide (mass ratio: 90/10) copolymer
having a number average molecular weight of 15000 was supplied at a
rate of 250 [g/min], and ethylene Glycol heated to 40.degree. C.
was supplied at a rate of 2.1 [g/min] to a single-screw extruder
having a diameter of 40 mm (L/D=40, preset temperature: 90.degree.
C.), and these were melt-mixed.
The mixture obtained from a discharge opening (the mixture was
discharged in a uniform and molten state, and it was confirmed
using an LC analysis that the mixture was mixed at the charge
ratio) was continuously supplied to a hopper port (preset
temperature: 80.degree. C.) of a twin-screw extruder having a
diameter of 30 mm (L/D=41.5). Simultaneously, dioctyltin dilaurate
was supplied to the hopper port of the twin-screw extruder at a
rate of 0.5 [g/min].
Separately, dicyclohexylmethane-4,4'-diisocyanate adjusted to
30.degree. C. was supplied to a screw barrel section situated on
the downstream side of the hopper port of the twin-screw extruder
at a rate of 12.4 [g/min] (R value=0.95), and was thereby caused to
continuously react under a nitrogen gas atmosphere (preset
temperature: 180.degree. C.). A strand obtained from the exit of
the twin-screw extruder was cooled, and was then pelletized (into
blocks each of 4.times.4.times.2.5 mm) by means of a pelletizer to
obtain a water-absorbent modified polyalkylene oxide.
The obtained water-absorbent modified polyalkylene oxide had a
water absorption ability of 20 [g/g], a ratio of the water-soluble
component of 11.3 [6 by mass], and a melt viscosity of 150
[Pas]
Production Example 3: Production of Water-Absorbent Modified
Polyalkylene Oxide
A polyethylene oxide having a number average molecular weight of
10000 was supplied at a rate of 200 [g/min], and 1,4-butanediol
heated to 40.degree. C. was supplied at a rate of 8.1 [g/min] to a
single-screw extruder having a diameter of 40 mm (L/D=40, preset
temperature: 90.degree. C.), and these were melt-mixed.
The mixture obtained from a discharge port (the mixture was
discharged in a uniform and molten state, and it was confirmed
using an LC analysis that the mixture were mixed at the charge
ratio) was continuously supplied to a hopper port (preset
temperature: 80.degree. C.) of a twin-screw extruder having a
diameter of 30 mm (L/D=41.5). Simultaneously, dioctyltin dilaurate
was supplied to the hopper port of the twin-screw extruder at a
rate of 0.5 [g/min]
Separately, dicyclohexylmethane-4,4'-diisocyanate adjusted to
30.degree. C. was supplied to a screw barrel section situated on
the downstream side of the hopper port of the twin-screw extruder
at a rate of 28.8 [g/min] (R value=1.00) and was caused to
continuously react in a nitrogen gas atmosphere (preset
temperature: 180.degree. C.). A strand obtained from an exit of the
twin-screw extruder was cooled and, then pelletized (into blocks
each of 4.times.4.times.2.5 mm) by means of a pelletizer to obtain
a water-absorbent modified polyalkylene oxide.
The obtained water-absorbent modified polyalkylene oxide had a
water absorption ability of 7 [g/g], a ratio of the water-soluble
component of 5.5 [% by mass], and a melt viscosity of 520 [Pas]
Production Example 4: Production of Water-Absorbent Modified
Polyalkylene Oxide
One hundred parts by mass of a fully dehydrated polyethylene oxide
having a number average molecular weight of 20000, 0.14 parts by
mass of 1,4-butanediol and 0.1 part by mass of dioctyltin dilaurate
were put at these ratios into storage tank A equipped with a
stirrer and held at 80.degree. C., and were stirred in a nitrogen
gas atmosphere to obtain a uniform mixture. Separately,
dicycrohexylmethane-4,4'-diisocyanate was put into storage tank B
held at 30.degree. C., and was stored in a nitrogen gas
atmosphere.
The mixture in storage tank A was continuously supplied at a rate
of 500 [g/min], and dicyclohexylmetahane-4,4'-disisocyanate in
storage tank B was continuously supplied at a rate of 7.2 [g/min]
to a twin-screw extruder set at 110 to 140.degree. C. (R
value=1.00) by means of a metering pump, and these were mixed in
the extruder to perform a reaction. A strand was discharged through
an exit of the extruder, and was pelletized (into blocks each of
4.times.4.times.2.5 mm) by means of a pelletizer to obtain a
water-absorbent modified polyalkylene oxide.
The obtained water-absorbent modified polyalkylene oxide had a
water absorption ability of 45 [g/g], a ratio of the water-soluble
component of 38.5 [1 by mass], and a melt viscosity of 300
[Pas]
TABLE-US-00001 TABLE 1 Polyalkylene Oxide Diol Used Used Amount
Type Amount Diisocyanate (parts by Molecular (carbon Molecular
Molar (parts by Molecular Type mass) Weight number) Weight
Ratio.sup.(1) mass) Type Weight Production EO 100 20000 4 90 2 0.9
HMDI 262 Example 1 Production EO/PO 250 15000 2 62 2 2.07 HMDI 262
Example 2 Production EO 200 10000 4 90 4.5 8.1 HMDI 262 Example 3
Production EO 100 20000 4 90 0.3 0.135 IPDI 222 Example 4
Diisocyanate Used Water Water Amount Absorption Soluble Melt (parts
by Ability Component Viscosity NCO/OH.sup.(2) mass) [g/g] [%] [Pa
s] Production 1 3.93 25 16.6 320 Example 1 Production 0.95 12.445
20 11.3 150 Example 2 Production 1 28.82 7 5.5 520 Example 3
Production 1 1.443 45 38.5 300 Example 4 .sup.(1)Molar ratio of
used amount of diol relative to 1 mol of polyalkylene oxide
.sup.(2)Ratio of molar number of NCO groups in diisocyanate
compound relative to total molar number of terminal OH groups in
polyalkylene oxide and OH groups in diol
Example 1
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 1 was supplied at 6 [kg/hr] and a
low-melting point polyamide resin [abbreviation: PAco, manufactured
by EMS-CHEMIE (Japan), Ltd., Griltex D1500A, melting point
95.degree. C., MFR=70 g/10 min (160.degree. C., 21.18 N), melt
viscosity 85 Pas] was supplied at 9 [kg/hr] to a twin-screw
extruder having a diameter of 28 mm (L/D=40) set at 110.degree. C.
to obtain a lubricating resin composition. The compositional ratios
of the lubricating resin composition are shown in Table 2.
The obtained lubricating resin composition was molded into a 10
cm.times.10 cm.times.0.1 cm sheet by means of a hot press
(manufactured by Gonna Hydraulic Press Manufacturing Co., Ltd.,
40-t press, pressure: 4.9 MPaG) set at 120.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size, and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 2.
Example 2
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 2 was supplied at 7 [kg/hr] and a
low-melting point polyamide resin [abbreviation: PAco, manufactured
by EMS-CHEMIE (Japan), Ltd., Griltex D1500A, melting point
95.degree. C., MFR=70 g/10 min (160.degree. C., 21.18 N), melt
viscosity 85 Pas] was supplied at 17.5 [kg/hr] to a twin-screw
extruder having a diameter of 28 mm (L/D=40) set at 120.degree. C.
to obtain a lubricating resin composition. The compositional ratios
of the lubricating resin composition are shown in Table 2.
The obtained lubricating resin composition was molded into a 10
cm.times.10 cm.times.0.1 cm sheet by means of a hot press
(manufactured by Gonno Hydraulic Press Manufacturing Co., Ltd.,
40-t press, pressure: 4.9 MPaG) set at 120.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 2.
Example 3
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 1 was supplied at 5 [kg/hr] and a
low-melting point polyamide resin [abbreviation: PAco, manufactured
by EMS-CHEMIE (Japan), Ltd., Griltex D1666A, melting point
85.degree. C., MFR=90 g/10 min (160.degree. C., 21.18 N), melt
viscosity 55 Pas] was supplied at 17.5 [kg/hr] to a twin-screw
extruder having a diameter of 28 mm (L/D=40) set at 130.degree. C.
to obtain a lubricating resin composition. The compositional ratios
of the lubricating resin composition are shown in Table 2.
The obtained lubricating resin composition was molded into a 10 cm
(W).times.10 cm (L).times.0.1 cm (T) sheet of the lubricating resin
composition by means of a hot press (manufactured by Gonno
Hydraulic Press Manufacturing Co., Ltd., 40-t press, pressure: 4.9
MPaG) set at 130.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 2.
Example 4
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 2 was supplied at 7.5 [kg/hr] and a
low-melting point polyamide resin [abbreviation: PAco, manufactured
by EMS-CHEMIE (Japan), Ltd., Griltex D1500A, melting point
95.degree. C., MFR=70 g/10 min (160.degree. C., 21.18 N), melt
viscosity 85 Pas] was supplied at 7.5 [kg/hr] to a twin-screw
extruder having a diameter of 28 mm (L/D=40) set at 120.degree. C.
to obtain a lubricating resin composition. The compositional ratios
of the lubricating resin composition are shown in Table 2.
The obtained lubricating resin composition was molded into a 10
cm.times.10 cm.times.0.1 cm sheet by means of a hot press
(manufactured by Gonna Hydraulic Press Manufacturing Co., Ltd.,
40-t press, pressure: 4.9 MPaG) set at 120.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 2.
Examples 5 to 7
Lubricating resin compositions were obtained in the same manner as
in Example 1 except that low-melting point polyamide resins
described below were used, that the preset temperature of the
twin-screw extruder having a diameter of 28 mm was changed to the
temperatures described below, and/or that the blending amount of
the low-melting point polyamide was changed as shown in Table
2.
Molding of the lubricating resin composition into the sheet and the
types of measurement and evaluation were executed in the same
manner as in Example 1 except that the pressing temperature was
changed to the values below.
Example 5
Low-Melting Point Polyamide Resin
[Abbreviation: PAco, manufactured by EMS-CHEMIE (Japan), Ltd.,
Griltex 1A, melting point 115.degree. C., MFR=16/10 min
(160.degree. C., 21.18 N), melt viscosity 120 Pas]
Preset Temperature of Twin-Screw Extruder: 140.degree. C.
Pressing Temperature: 140.degree. C.
Example 6
Low-Melting Point Polyamide Resin
[Abbreviation: PAco, manufactured by EMS-CHEMIE (Japan), Ltd.,
Griltex 2A, melting point 130.degree. C., MFR=18 g/10 min
(160.degree. C., 21.18 N), melt viscosity 135 Pas]
Preset Temperature of Twin-Screw Extruder: 140.degree. C.
Pressing Temperature: 140.degree. C.
Example 7
Low-Melting Point Polyamide Resin
[Abbreviation: PAco, manufactured by EMS-CHEMIE (Japan), Ltd.,
Griltex D1500A, melting point 95.degree. C., MFR=70 g/10 min
(160.degree. C., 21.18 N), melt viscosity 85 Pas]
Preset Temperature of Twin-Screw Extruder: 120.degree. C.
Pressing Temperature: 120.degree. C.
Comparative Example 1
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 1 was supplied at 12.5 [kg/hr] and
a low-melting point polyamide resin [abbreviation: PAco,
manufactured by EMS-CHEMIE (Japan), Ltd., Griltex D1500A, melting
point 95.degree. C., MFR=70 g/10 min (160.degree. C., 21.18 N),
melt viscosity 85 Pas] was supplied at 2.5 [kg/hr] to a twin-screw
extruder having a diameter of 28 mm set at 120.degree. C. to obtain
a lubricating resin composition. The compositional ratios of the
lubricating resin composition are shown in Table 3.
The obtained lubricating resin composition was molded into a 6 cm
(W).times.9 cm (L).times.0.15 cm (T) sheet of the lubricating resin
composition by means of an injection-molding machine (manufactured
by Toyo Machinery and Metal Co., Ltd., Model: T180G2) set at 130 to
150.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 3.
Comparative Example 2
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 2 was supplied at 6 [kg/hr] and an
ethylene/vinyl acetate copolymer [abbreviation: EVA, manufactured
by Du Pont-Mitsui Fluorochemicals Co, Ltd.: Evaflex EV150, vinyl
acetate content=33%, melting point=MFR=30 g/10 min (190.degree. C.,
21.18 N), melt viscosity 170 Pas] was supplied at 15 [kg/hr] to a
twin-screw extruder having a diameter of 28 mm (L/D=40) set at
140.degree. C. to obtain a lubricating resin composition. The
compositional ratios of the lubricating resin composition are shown
in Table 3.
The obtained lubricating resin composition was molded into a 10 cm
(W).times.10 cm (L).times.0.1 cm (T) sheet of the lubricating resin
composition by means of the hot press (manufactured by Gonno
Hydraulic Press Manufacturing Co., Ltd., 40-t press, pressure: 4.9
MPaG) set at 150.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 3.
Comparative Example 3
A water-absorbent modified polyalkylene oxide obtained in the same
manner as in Production Example 2 was supplied at 6 [kg/hr] and a
high impact polystyrene [abbreviation: HIPS, manufactured by PS
Japan Corporation, MFR=18 g/10 min (200.degree. C., 49.03 N), melt
viscosity unmeasurable] was supplied at 15 [kg/hr] to a twin-screw
extruder having a diameter of 28 mm (L/D=40) set at 220.degree. C.
to obtain a lubricating resin composition. The compositional ratios
of the lubricating resin composition are shown in Table 3.
The obtained lubricating resin composition was molded into a 10 cm
(W).times.10 cm (L).times.0.1 cm (T) sheet of the lubricating resin
composition by means of a hot press (manufactured by Gonno
Hydraulic Press Manufacturing Co., Ltd., 40-t press, pressure: 4.9
MPaG) set at 220.degree. C.
The obtained sheet of the lubricating resin composition was cut
into a predetermined size and the above various types of
measurement and evaluation were executed therefor. The results
thereof are shown in Table 3.
Comparative Examples 4 to 7
Lubricating resin compositions were obtained in the same manner as
in Example 1 except that the modified polyalkylene oxide was
changed to those obtained in Production Examples described in Table
3, that low-melting point polyamide resins described below were
used, that the preset temperature of the twin-screw extruder having
a diameter of 28 mm was changed to the values described below,
and/or that the blending amount of the low-melting point polyamide
was changed to values shown in Table 3.
Molding of the lubricating resin composition into the sheet and the
types of measurement and evaluation were executed in the same
manner as in Example 1 except that the pressing temperature was
changed to the values below.
Comparative Example 4
Modified Polyalkylene Oxide: Production Example 3
Low-Melting Point Polyamide Resin
[abbreviation: PAco, manufactured by EMS-CHEMIE (Japan), Ltd.,
Griltex D1500A, melting point 95.degree. C., MFR=70 g/10 min
(160.degree. C., 21.18 N), melt viscosity 85 Pas]
Preset Temperature of Twin-Screw Extruder: 120.degree. C.
Pressing Temperature: 120.degree. C.
Comparative Example 5
Modified Polyalkylene Oxide: Production Example 4
Low-Melting Point Polyamide Resin
[abbreviation: PAco, manufactured by EMS-CHEMIE (Japan), Ltd.,
Griltex D1500A, melting point 95.degree. C., MFR=70 g/10 min
(160.degree. C., 21.18 N), melt viscosity 85 Pas]
Preset Temperature of Twin-Screw Extruder: 120.degree. C.
Pressing Temperature: 120.degree. C.
Comparative Example 6
Modified Polyalkylene Oxide: Production Example 1
Polyamide Resin
[abbreviation: PAco, manufactured by Toray Industries, Inc., Amilan
CM6041CF melting point 194.degree. C., melt viscosity
unmeasurable]
Preset Temperature of Twin-Screw Extruder: 220.degree. C.
Pressing Temperature: 220.degree. C.
Comparative Example 7
Modified Polyalkylene Oxide: Production Example 1
Low-Melting Point Polyamide Resin
[abbreviation: PAco, manufactured by EMS-CHEMIE (Japan), Ltd.,
Griltex D1500A, melting point 95.degree. C., MFR=70 g/10 min
(160.degree. C., 21.18 N), melt viscosity 85 Pas]
Preset Temperature of Twin-Screw Extruder: 120.degree. C.
Pressing Temperature: 120.degree. C.
TABLE-US-00002 TABLE 2 Modified Polyalkylene Oxide Water
Thermostatic Resin.sup.1) Absorption Melt Melting Melt (parts
Swelling Thickness Ability Viscosity Point MFR Viscosity by Ratio
Variation Slimy Type [g/g] [Pa s] Type (.degree. C.) [g/10 min] [Pa
s] mass).sup.2) (%) [times] Feeling Example 1 Production 25 320
PAco 95 70 85 180 370 2.5 A Example 1 (160.degree. C., 21.18N)
Example 2 Production 20 150 PAco 95 70 85 250 170 1.8 A Example 2
(160.degree. C., 21.18N) Example 3 Production 25 320 PAco 85 80 85
350 120 1.2 A Example 1 (160.degree. C., 21.18N) Example 4
Producation 20 180 PAco 95 20 85 100 480 3.5 A Example 2
(160.degree. C., 21.18N) Example 5 Production 25 320 PAco 115 18
120 150 300 1.8 A Example 1 (160.degree. C., 21.18N) Example 6
Production 25 320 PAco 130 18 135 150 280 1.5 A Example 1
(160.degree. C., 21.18N) Example 7 Production 25 280 PAco 95 70 85
50 480 3.6 A Example 1 (160.degree. C., 21.18N) Friction Physical
Property Mass Coefficient of Friction (MU) Deviation on Mass
Coefficient of Friction (MMD) (Lubricity) (Roughness Resistant
Property) First Time Sixth Time First Time Sixth Time 30 sec 5 min
10 min 30 sec 8 min 10 min 30 sec 5 min 10 min 30 sec 5 min 10 min
Example 1 0.01 0.01 0.01 0.01 0.01 0.01 0.004 0.004 0.004 0.004
0.004 0.00- 4 Example 2 0.015 0.015 0.015 0.015 0.015 0.015 0.009
0.009 0.009 0.009 0.00- 9 0.009 Example 3 0.02 0.02 0.02 0.02 0.02
0.02 0.008 0.008 0.008 0.008 0.008 0.00- 8 Example 4 0.01 0.01 0.01
0.01 0.01 0.01 0.008 0.008 0.008 0.008 0.008 0.00- 6 Example 5
0.013 0.013 0.013 0.013 0.013 0.013 0.009 0.009 0.009 0.009 0.00- 9
0.009 Example 6 0.015 0.015 0.015 0.015 0.015 0.015 0.008 0.008
0.008 0.008 0.00- 8 0.008 Example 7 0.01 0.01 0.01 0.01 0.01 0.01
0.008 0.008 0.008 0.008 0.008 0.00- 8 .sup.1)PAco: Copolymerized
Nylon, EVA: Ethylene/Vinyl Acetate Copolymer: HIPS: High Impact
Polystyrene .sup.2)Parts by mass of thermoplastic resin relative to
100 parts by mass of modified polyalkyline oxide
TABLE-US-00003 TABLE 3 Modified Polyalkylene Oxide Water
Thermostatic Resin.sup.1) Absorption Melt Melting Melt (parts
Swelling Thickness Ability Viscosity Point MFR Viscosity by Ratio
Variation Slimy Type [g/g] [Pa s] Type (.degree. C.) [g/10 min] [Pa
s] mass).sup.2) (%) [times] Feeling Comparative Production 25 320
PAco 95 70 85 20 1250 3.3 A Example 1 Example 1 (160.degree. C.,
21.18N) Comparative Production 20 150 EVA -- 30 170 250 250 2.5 A
Example 2 Example 2 (190.degree. C., 21.18N) Comparative Production
20 150 HIPS -- 18 -- 250 110 1.1 A Example 3 Example 1 (200.degree.
C., 85 49.03N) Comparative Producation 7 150 PAco 93 70 85 150 110
1.1 A Example 4 Example 2 (160.degree. C., 21.18N) Comparative
Production 45 300 PAco 95 70 85 150 550 4.2 C Example 5 Example 1
(160.degree. C., 21.18N) Comparative Production 25 320 PAco 194 --
-- 150 100 1.1 A Example 6 Example 1 Comparative Production 25 320
PAco 95 70 85 550 110 1.1 A Example 7 Example 1 (160.degree. C.,
21.18N) Friction Physical Property Mass Coefficient of Friction
(MU) Deviation on Mass Coefficient of Friction (MMD) (Lubricity)
(Roughness Resistant Property) First Time Sixth Time First Time
Sixth Time 30 sec 5 min 10 min 30 sec 5 min 10 min 30 sec 5 min 10
min 30 sec 5 min 10 min Comparative 0.01 0.01 0.01 0.01 0.01 0.01
0.009 0.009 0.009 0.009 0.009 0- .009 Example 1 Comparative 0.12
0.16 0.23 0.18 0.17 0.23 0.03 0.05 0.06 0.04 0.06 0.07 Example 2
Comparative 0.15 0.22 0.25 0.16 0.25 0.28 0.02 0.05 0.06 0.03 0.04
0.07 Example 3 Comparative 0.2 0.23 0.3 0.23 0.25 0.33 0.02 0.04
0.05 0.03 0.05 0.08 Example 4 Comparative 0.011 0.011 0.011 0.15
0.15 0.15 0.008 0.008 0.009 0.03 0.03 - 0.03 Example 5 Comparative
0.11 0.11 0.11 0.12 0.12 0.12 0.01 0.01 0.01 0.01 0.01 0.01 Example
6 Comparative 0.11 0.11 0.11 0.12 0.12 0.12 0.01 0.01 0.01 0.01
0.01 0.01 Example 7 .sup.1)Paco: Copolymerized Nylon, EVA:
Ethylene/Vinyl Acetate Copolymer: HIPS: High Impact Polystyrene
.sup.2)Parts by mass of thermoplastic resin relative to 100 parts
by mass of modified polyalkyline oxide
As is apparent from the results shown in Tables 2 and 3, the
lubricating resin compositions of the present invention comprising
each certain amounts of the water-absorbent modified polyalkylene
oxide and the low-melting point polyamide resin have small
variation in dimension due to swelling, and maintain the lubricity
thereof and have no variation in roughness resistant property even
under a wet condition, under a dry condition or during repeated use
thereof.
INDUSTRIAL APPLICABILITY
The lubricating resin composition according to the present
invention maintains its lubricity and represents no slimy feeling
even under a wet or dry condition or during repeated use thereof,
and can thus be suitably used in a wide field in which lubricity
under a wet condition is necessary, for example, personal care
items such as wet shaving instruments typified by a razor, and a
catheter.
* * * * *